Microemulsion all purpose liquid cleaning compositions comprising partially esterified, fully esterified and non-esterified polyhydric alcohol and grease release agent

ABSTRACT

An improvement is described in all purpose liquid cleaning composition and microemulsion composition which are especially effective in the removal of oily and greasy soil and also exhibiting a grease release effect, containing an anionic detergent, a supplemental grease release agent, a partially esterfied ethoxylated polyhydric type alcohol, a hydrocarbon ingredient, and water which can comprise the use of a water-insoluble odoriferous perfume as the essential hydrocarbon ingredient.

RELATED APPLICATION

This application is a continuation-in-part application of U.S. Ser. No.8/336,934 filed Nov. 15, 1994 now abandoned which in turn is acontinuation-in-part application of U.S. Ser. No. 8/288,638 filed Aug.10, 1994 now abandoned which in turn is a continution-in-partapplication of U.S. Ser. No. 8/155,345 filed Nov. 22, 1993 now abandonedwhich is a continuation-in-part application of U.S. Ser. No. 8/102,314filed Aug. 4, 1993 now abandoned.

FIELD OF THE INVENTION

The present invention relates to an all purpose cleaning ormicroemulsion composition containing a grease release system comprisingan ethoxylated polyhydric alcohol type compound as defined below andoptionally, a grease release agent.

BACKGROUND OF THE INVENTION

This invention relates to an improved all-purpose liquid cleaningcomposition or a microemulsion composition designed in particular forcleaning hard surfaces and which is effective in removing grease soiland/or bath soil and in leaving unrinsed surfaces with a shinyappearance.

In recent years all-purpose liquid detergents have become widelyaccepted for cleaning hard surfaces, e.g., painted woodwork and panels,tiled walls, wash bowls, bathtubs, linoleum or tile floors, washablewall paper, etc.. Such all-purpose liquids comprise clear and opaqueaqueous mixtures of water-soluble synthetic organic detergents andwater-soluble detergent builder salts. In order to achieve comparablecleaning efficiency with granular or powdered all-purpose cleaningcompositions, use of water-soluble inorganic phosphate builder salts wasfavored in the prior art all-purpose liquids. For example, such earlyphosphate-containing compositions are described in U.S. Pat. Nos.2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.

In view of the environmentalist's efforts to reduce phosphate levels inground water, improved all-purpose liquids containing reducedconcentrations of inorganic phosphate builder salts or non-phosphatebuilder salts have appeared. A particularly useful self-opacified liquidof the latter type is described in U.S. Pat. No. 4,244,840.

However, these prior art all-purpose liquid detergents containingdetergent builder salts or other equivalent tend to leave films, spotsor streaks on cleaned unrinsed surfaces, particularly shiny surfaces.Thus, such liquids require thorough rinsing of the cleaned surfaceswhich is a time-consuming chore for the user.

In order to overcome the foregoing disadvantage of the prior artall-purpose liquid, U.S. Pat. No. 4,017,409 teaches that a mixture ofparaffin sulfonate and a reduced concentration of inorganic phosphatebuilder salt should be employed. However, such compositions are notcompletely acceptable from an environmental point of view based upon thephosphate content. On the other hand, another alternative to achievingphosphate-free all-purpose liquids has been to use a major proportion ofa mixture of anionic and nonionic detergents with minor amounts ofglycol ether solvent and organic amine as shown in U.S. Pat. No.3,935,130. Again, this approach has not been completely satisfactory andthe high levels of organic detergents necessary to achieve cleaningcause foaming which, in turn, leads to the need for thorough rinsingwhich has been found to be undesirable to today's consumers.

Another approach to formulating hard surfaced or all-purpose liquiddetergent composition where product homogeneity and clarity areimportant considerations involves the formation of oil-in-water (o/w)microemulsions which contain one or more surface-active detergentcompounds, a water-immiscible solvent (typically a hydrocarbon solvent),water and a "cosurfactant" compound which provides product stability. Bydefinition, an o/w microemulsion is a spontaneously forming colloidaldispersion of "oil" phase particles having a particle size in the rangeof 25 to 800 Å, in a continuous aqueous phase.

In view of the extremely fine particle size of the dispersed oil phaseparticles, microemulsions are transparent to light and are clear andusually highly stable against phase separation.

Patent disclosures relating to use of grease-removal solvents in o/wmicroemulsions include, for example, European Patent Applications EP0137615 and EP 0137616--Herbots et al; European Patent Application EP0160762--Johnston et al; and U.S. Pat. No. 4,561,991--Harbors et al.Each of these patent disclosures also teaches using at least 5% byweight of grease-removal solvent.

It also is known from British Patent Application GB 2144763A to Harborset al, published Mar. 13, 1985, that magnesium salts enhancegrease-removal performance of organic grease-removal solvents, such asthe terpenes, in o/w microemulsion liquid detergent compositions. Thecompositions of this invention described by Herbots et al. require atleast 5% of the mixture of grease-removal solvent and magnesium salt andpreferably at least 5% of solvent (which may be a mixture ofwater-immiscible non-polar solvent with a sparingly soluble slightlypolar solvent) and at least 0.1% magnesium salt.

However, since the amount of water immiscible and sparingly solublecomponents which can be present in an o/w microemulsion, with low totalactive ingredients without impairing the stability of the microemulsionis rather limited (for example, up to 18% by weight of the aqueousphase), the presence of such high quantities of grease-removal solventtend to reduce the total amount of greasy or oily soils which can betaken up by and into the microemulsion without causing phase separation.

The following representative prior art patents also relate to liquiddetergent cleaning compositions in the form of o/w microemulsions: U.S.Pat. Nos. 4,472,291--Rosario; 4,540,448--Gauteer et al;3,723,330--Sheflin; etc.

Liquid detergent compositions which include terpenes, such asd-limonene, or other grease-removal solvent, although not disclosed tobe in the form of o/w microemulsions, are the subject matter of thefollowing representative patent documents: European Patent Application0080749; British Patent Specification 1,603,047; and U.S. Pat. Nos.4,414,128 and 4,540,505. For example, U.S. Pat. No. 4,414,128 broadlydiscloses an aqueous liquid detergent composition characterized by, byweight:

(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric orzwitterionic surfactant or mixture thereof;

(b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, ata weight ratio of (a):(b) being in the range of 5:1 to 1:3; and

(c) from 0.5% 10% of a polar solvent having a solubility in water at 15°C. in the range of from 0.2% to 10%. Other ingredients present in theformulations disclosed in this patent include from 0.05% to 2% by weightof an alkali metal, ammonium or alkanolammonium soap of a C₁₃ -C₂₄ fattyacid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueoussolvent, e.g., alcohols and glycol ethers, up to 10% by weight; andhydrotropes, e.g., urea, ethanolamines, salts of lower alkylarylsulfonates, up to 10% by weight. All of the formulations shown in theExamples of this patent include relatively large amounts of detergentbuilder salts which are detrimental to surface shine.

Furthermore, the present inventors have observed that in formulationscontaining grease-removal assisting magnesium compounds, the addition ofminor amounts of builder salts, such as alkali metal polyphosphates,alkali metal carbonates, nitrilotriacetic acid salts, and so on, tendsto make it more difficult to form stable microemulsion systems.

U.S. Pat. No. 5,082,584 discloses a microemulsion composition having ananionic surfactant, a cosurfactant, nonionic surfactant, perfume andwater; however, these compositions do not possess the ecotoxicity andthe improved interfacial tension properties as exhibited by thecompositions of the instant invention.

A number of patents teach esterified ethoxylated glycerol compounds forvarious applications. These patents are Great Britain 1,453,385; Japan59-1600 and Japan 58-206693 and European Patent Application 0586,323A1.These publications fail to appreciate that a mixture of esterifiedethoxylated glycerol and nonesterified ethoxylated glycerol, when usedin a hard surface cleaning composition, functions as a grease releaseagent.

SUMMARY OF THE INVENTION

The present invention provides an improved, clear, liquid cleaningcomposition having improved interfacial tension which improves cleaninghard surface in the form of a microemulsion which is suitable forcleaning hard surfaces such as plastic, vitreous and metal surfaceshaving a shiny finish, oil stained floors, automative engines and otherengines. More particularly, the improved cleaning compositions exhibitgood grease soil removal properties due to the improved interfacialtensions, when used in undiluted (neat) form and leave the cleanedsurfaces shiny without the need of or requiring only minimal additionalrinsing or wiping. The latter characteristic is evidenced by little orno visible residues on the unrinsed cleaned surfaces and, accordingly,overcomes one of the disadvantages of prior art products. The instantcompositions exhibit a grease release effect in that the instantcompositions impede or decrease the anchoring of greasy soil on surfacesthat have been cleaned with the instant compositions as compared tosurfaces cleaned with a commercial microemulsion composition which meansthat the grease soiled surface is easier to clean upon subsequentcleanings.

Surprisingly, these desirable results are accomplished even in theabsence of polyphosphate or other inorganic or organic detergent buildersalts and also in the complete absence or substantially complete absenceof grease-removal solvent.

The instant compositions are more friendly for the environment due tothe low ecotoxicity of ethoxylated polyhydric alcohol type compound suchas an ethoxylated glycerol type compound as defined below used in theinstant compositions.

The compositions of the instant invention have an ecotoxocity value asmeasured by the LC 50 test as deferred by The Organization for EconomicCooperation and Development (OECD)(of which the United States is amember) in OECD Test No. 202 of at least 0.18 ml/L measured on Daphniaemicroorganisms.

In one aspect, the invention generally provides a stable, opticallyclear microemulsion, hard surface cleaning composition especiallyeffective in the removal of oily and greasy oil, which is in the form ofa substantially dilute oil-in-water microemulsion having an aqueousphase and an oil phase. The dilute microemulsion composition includes,on a weight basis:

0.1% to 20% of an anionic surfactant;

0 to 10%, more preferably 0.1% to 10% of a supplemental grease releaseagent;

0.1% to 50% of a water-mixable cosurfactant having either limitedability or substantially no ability to dissolve oily or greasy soil;

0.1% to 10% of a compound which is a mixture of a partially esterifiedethoxylated polyhydric alcohol, a fully esterified ethoxylatedpolyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol(said mixture being herein after referred to as an ethoxylatedpolyhydric alcohol type compound such as an ethoxylated glycerol typecompound);

0 to 15% of magnesium sulfate heptahydrate;

0.4 to 10.0% of a perfume, essential oil, or water insoluble hydrocarbonhaving 6 to 18 carbon atoms; and

the balance being water.

Quite surprisingly although the perfume is not, per se, a solvent forgreasy or oily soil, - - - even though some perfumes may, in fact,contain as much as 80% of terpenes which are known as good greasesolvents - - - the inventive compositions in dilute form have thecapacity to solubilize up to 10 times or more of the weight of theperfume of oily and greasy soil, which is removed or loosened from thehard surface by virtue of the action of the anionic and nonionicsurfactants, said soil being taken up into the oil phase of the o/wmicroemulsion.

In a second aspect, the invention comprises an all purpose hard surfacecleaning composition comprising approximately by weight:

0.1% to 20% of an anionic surfactant;

0 to 10%, more preferably 0.1% to 10% of a supplemental grease releaseagent;

0 to 50%, more preferably 0.1% to 50% of a water-mixable cosurfactant;

0.1% to 10% of said ethoxylated polyhydric alcohol type compound;

0 to 15% of magnesium sulfate heptahydrate;

0 to 10%, more preferably 0.1% to 10% of a perfume, essential oil orwater insoluble hydrocarbon having 6 to 18 carbon atoms; and

the balance being water.

In a third aspect, the invention generally provides highly concentrationmicroemulsion compositions in the form of either an oil-in-water (o/w)microemulsion or a water-in-oil (w/o) microemulsion which when dilutedwith additional water before use can form dilute o/w microemulsioncompositions. Broadly, the concentrated microemulsion compositionscontain, by weight, 0.1% to 30% of an anionic surfactant, 0.1% to 10% ofsaid ethoxylated polyhydric alcohol type compound, 0.4% to 10% ofperfume, essential oil or water insoluble hydrocarbon having 6 to 18carbon atoms, 0.1% to 50% of a cosurfactant, 0 to 10%, more preferably0.1% to 10% of a grease release agent and the balance being water.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a stable optically clear microemulsioncomposition comprising approximately by weight: 0.1% to 20% of ananionic surfactant, 0.1% to 50% of a cosurfactant, 0 to 10.0%, morepreferably 0.1% to 10% of a supplemental grease release agent, 0.1% to10% of an ethoxylated polyhydric alcohol type compound, 0.4% to 10% of awater insoluble hydrocarbon, essential oil or a perfume and the balancebeing water, said composition having an ecotoxocity value as measured bythe LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms.

The present invention also relates to a stable optically clearconcentrated microemulsion composition comprising approximately byweight 0.1% to 30% of an anionic surfactant; 0.1% to 10% of saidethoxylated polyhydric alcohol type compound; 0.4% to 10% of a perfume,essential oil or water insoluble hydrocarbon having 6 to 18 carbonatoms; 0.1 to 50% of a cosurfactant; 0 to 10%, more preferably 0.1% to10% of a supplemental grease release agent and the balance being water.

The present invention also relates to all purpose hard surface cleaningcomposition comprising approximately by weight 0.1% to 20% of an anionicsurfactant, 0 to 10%, more preferably 0.1% to 10% of a supplementalgrease agent, 0 to 50%, more preferably 0.1% to 50% of a water mixablecosurfactant, 0.1% to 10% of said ethoxylated polyhydric alcohol typecompound, 0 to 15% of magnesium sulfate heptahydrate, 0 to 10%, morepreferably 0.1 to 10% of a perfume, essential oil or water insolublehydrocarbon having 6 to 18 carbon atoms and the balance being water.

According to the present invention, the role of the water insolublehydrocarbon can be provided by a non-water-soluble perfume. Typically,in aqueous based compositions the presence of a solubilizers, such asalkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine,urea, etc., is required for perfume dissolution, especially at perfumelevels of 1% and higher, since perfumes are generally a mixture offragrant essential oils and aromatic compounds which are generally notwater-soluble. Therefore, by incorporating the perfume into the aqueouscleaning composition as the oil (hydrocarbon) phase of the ultimate o/wmicroemulsion composition, several different important advantages areachieved.

First, the cosmetic properties of the ultimate cleaning composition areimproved: the compositions are both clear (as a consequence of theformation of a microemulsion) and highly fragranced (as a consequence ofthe perfume level).

Second, the need for use of solubilizers, which do not contribute tocleaning performance, is eliminated.

Third, an improved grease release effect and an improved grease removalcapacity in neat (undiluted) usage of the dilute aspect or afterdilution of the concentrate can be obtained without detergent buildersor buffers or conventional grease removal solvents at neutral or acidicpH and at low levels of active ingredients while improved cleaningperformance can also be achieved in diluted usage.

The use of 0.1 to 10 wt. % of the ethoxylated polyhydric alcohol typecompound in combination optionally with 0 to 10 wt. %, more preferably0.1 wt. % to 10.0 wt. % of a supplemental grease release agent in theinstant composition yields a composition having excellent grease soilrelease properties, when the composition is used in neat or dilute form.

As used herein and in the appended claims the term "perfume" is used inits ordinary sense to refer to and include any non-water solublefragrant substance or mixture of substances including natural (i.e.,obtained by extraction of flower, herb, blossom or plant), artificial(i.e., mixture of natural oils or oil constituents) and syntheticallyproduced substance) odoriferous substances. Typically, perfumes arecomplex mixtures of blends of various organic compounds such asalcohols, aldehydes, ethers, aromatic compounds and varying amounts ofessential oils (e.g., terpenes) such as from 0% to 80%, usually from 10%to 70% by weight, the essential oils themselves being volatileodoriferous compounds and also serving to dissolve the other componentsof the perfume.

In the present invention the precise composition of the perfume is of noparticular consequence to cleaning performance so long as it meets thecriteria of water immiscibility and having a pleasing odor. Naturally,of course, especially for cleaning compositions intended for use in thehome, the perfume, as well as all other ingredients, should becosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.. Theinstant compositions show a marked improvement in ecotoxocity ascompared to existing commercial products.

The hydrocarbon such as a perfume is present in the dilute o/wmicroemulsion in an amount of from 0.4% to 10% by weight, preferablyfrom 0.4% to 3.0% by weight, especially preferably from 0.5% to 2.0% byweight, such as weight percent. If the amount of hydrocarbon (perfume)is less than 0.4% by weight it becomes difficult to form the o/wmicroemulsion. If the hydrocarbon (perfume) is added in amounts morethan 10% by weight, the cost is increased without any additionalcleaning benefit and, in fact, with some diminishing of cleaningperformance insofar as the total amount of greasy or oily soil which canbe taken up in the oil phase of the microemulsion will decreaseproportionately. In the all purpose hard surface cleaning compositionwhich is not a microemulsion the concentration of the perfume is 0 to 10wt. %, more preferably 0.1 wt. % to 10wt. %

Furthermore, although superior grease removal performance will beachieved for perfume compositions not containing any terpene solvents,it is apparently difficult for perfumers to formulate sufficientlyinexpensive perfume compositions for products of this type (i.e., verycost sensitive consumer-type products) which includes less than 20%,usually less than 30%, of such terpene solvents.

Thus, merely as a practical matter, based on economic consideration, thedilute microemulsion detergent cleaning compositions of the presentinvention may often include as much as 0.2% to 7% by weight, based onthe total composition, of terpene solvents introduced thereunto via theperfume component. However, even when the amount of terpene solvent inthe cleaning formulation is less than 1.5% by weight, such as up to 0.6%by weight or 0.4% by weight or less, satisfactory grease removal and oilremoval capacity is provided by the inventive diluted o/wmicroemulsions.

Thus, for a typical formulation of a diluted microemulsion according tothis invention a 20 milliliter sample of microemulsion containing 1% byweight of perfume will be able to solubilize, for example, up to 2 to 3ml of greasy and/or oily soil, while retaining its form as amicroemulsion, regardless of whether the perfume contains 0%, 0.1%,0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% by weight of terpene solvent.In other words, it is an essential feature of the compositions of thisinvention that grease removal is a function of the result of themicroemulsion, per se, and not of the presence or absence in themicroemulsion of a "greasy soil removal" type of solvent.

In place of the perfume in either the microemulsion composition or theall purpose hard surface cleaning composition at the same previouslydefined concentrations that the perfume was used in either themicroemulsion or the all purpose hard surface cleaning composition onecan employ an essential oil or a water insoluble hydrocarbon having 6 to18 carbon such as a paraffin or isoparaffin.

Suitable essential oils are selected from the group consisting of:Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand,Balsam (Peru), Basil oil (India), Black pepper oil, Black pepperoleoresin 40/20, Bols de Rose (Brazil) FOB, Borneol Flakes (China),Camphor oil, White, Camphor powder synthetic technical, Cananga oil(Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP,Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil,Clove leaf, Coriander (Russia), Coumarin 69° C. (China), CyclamenAldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil,Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Gingeroleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam,Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil,L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oildistilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methylcedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Muskketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermintoil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin,Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmintoil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java),Wintergreen

Regarding the anionic surfactant present in the o/w microemulsions anyof the conventionally used water-soluble anionic surfactants or mixturesof said anionic surfactants and anionic surfactants can be used in thisinvention. As used herein the term "anionic surfactant" is intended torefer to the class of anionic and mixed anionic-nonionic detergentsproviding detersive action.

The water-soluble organic surfactant materials which are used in formingthe ultimate o/w microemulsion compositions of this invention may beselected from the group consisting of water-soluble, non-soap, anionicsurfactants mixed with a fatty acid and a partially esterfiedethoxylated glycerol.

Suitable water-soluble non-soap, anionic surfactants include thosesurface-active or detergent compounds which contain an organichydrophobic group containing generally 8 to 26 carbon atoms andpreferably 10 to 18 carbon atoms in their molecular structure and atleast one water-solubilizing group selected from the group of sulfonate,sulfate and carboxylate so as to form a water-soluble detergent.Usually, the hydrophobic group will include or comprise a C₈ -C₂₂ alkyl,alkyl or acyl group. Such surfactants are employed in the form ofwater-soluble salts and the salt-forming cation usually is selected fromthe group consisting of sodium, potassium, ammonium, magnesium andmono-, di- or tri-C₂ -C₃ alkanolammonium, with the sodium, magnesium andammonium cations again being preferred.

Examples of suitable sulfonated anionic surfactants are the well knownhigher alkyl mononuclear aromatic sulfonates such as the higher alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the higheralkyl group in a straight or branched chain, C₈ -C₁₅ alkyl toluenesulfonates and C₈ -C₁₅ alkyl phenol sulfonates.

A preferred sulfonate is linear alkyl benzene sulfonate having a highcontent of 3- (or higher) phenyl isomers and a correspondingly lowcontent (well below 50%) of 2- (or lower) phenyl isomers, that is,wherein the benzene ring is preferably attached in large part at the 3or higher (for example, 4, 5, 6 or 7) position of the alkyl group andthe content of the isomers in which the benzene ring is attached in the2 or 1 position is correspondingly low. Particularly preferred materialsare set forth in U.S. Pat. No. 3,320,174.

Other suitable anionic surfactants are the olefin sulfonates, includinglong-chain alkene sulfonates, long-chain hydroxyalkane sulfonates ormixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefinsulfonate detergents may be prepared in a known manner by the reactionof sulfur trioxide (SO₃) with long-chain olefins containing 8 to 25,preferably 12 to 21 carbon atoms and having the formula RCH═CHR₁ where Ris a higher alkyl group of 6 to 23 carbons and R₁ is an alkyl group of 1to 17 carbons or hydrogen to form a mixture of sultones and alkenesulfonic acids which is then treated to convert the sultones tosulfonates. Preferred olefin sulfonates contain from 14 to 16 carbonatoms in the R alkyl group and are obtained by sulfonating an a-olefin.

Other examples of suitable anionic sulfonate surfactants are theparaffin sulfonates containing 10 to 20, preferably 13 to 17, carbonatoms. Primary paraffin sulfonates are made by reacting long-chain alphaolefins and bisulfites and paraffin sulfonates having the sulfonategroup distributed along the paraffin chain are shown in U.S. Pat. Nos.2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.

Examples of satisfactory anionic sulfate surfactants are the C₈ -C₁₈alkyl sulfate salts and the C₈ -C₁₈ alkyl sulfate salts and the C₈ -C₁₈alkyl ether polyethenoxy sulfate salts having the formula R(OC₂ H₄)_(n)OSO₃ M wherein n is 1 to 12, preferably 1 to 5, and M is a solubilizingcation selected from the group consisting of sodium, potassium,ammonium, magnesium and mono-, di- and triethanol ammonium ions. Thealkyl sulfates may be obtained by sulfating the alcohols obtained byreducing glycerides of coconut oil or tallow or mixtures thereof andneutralizing the resultant product.

The alkyl sulfates may be obtained by sulfating the alcohols obtained byreducing glycerides of coconut oil or tallow or mixtures thereof andneutralizing the resultant product. On the other hand, the alkyl etherpolyethenoxy sulfates are obtained by sulfating the condensation productof ethylene oxide with a C₈ -C₁₈ alkanol and neutralizing the resultantproduct. The alkyl ether polyethenoxy sulfates differ from one anotherin the number of moles of ethylene oxide reacted with one mole ofalkanol. Preferred alkyl sulfates and preferred alkyl ether polyethenoxysulfates contain 10 to 16 carbon atoms in the alkyl group.

The C₈ -C₁₂ alkylphenyl ether polyethenoxy sulfates containing from 2 to6 moles of ethylene oxide in the molecule also are suitable for use inthe inventive compositions. These surfactants can be prepared byreacting an alkyl phenol with 2 to 6 moles of ethylene oxide andsulfating and neutralizing the resultant ethoxylated alkylphenol.

Other suitable anionic detergents are the C₉ -C₁₅ alkyl etherpolyethenoxyl carboxylates having the structural formula R(OC₂ H₄)_(n)OX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X isselected from the group consisting of CH₂, C(O)R₁ and ##STR1## whereinR₁ is a C₁ -C₃ alkylene group. Preferred compounds include C₉ -C₁₁ alkylether polyethenoxy (7-9) C(O) CH₂ CH₂ COOH, C₁₃ -C₁₅ alkyl etherpolyethenoxy (7-9) ##STR2## and C₁₀ -C₁₂ alkyl ether polyethenoxy (5-7)CH₂ COOH. These compounds may be prepared by condensing ethylene oxidewith appropriate alkanol and reacting this reaction product withchloracetic acid to make the ether carboxylic acids as shown in U.S.Pat. No. 3,741,911 or with succinic anhydride or phtalic anhydride.

Obviously, these anionic detergents will be present either in acid formor salt form depending upon the pH of the final composition, with thesalt forming cation being the same as for the other anionic detergents.

Of the foregoing non-soap anionic surfactants, the preferred surfactantsare the C₉ -C₁₅ linear alkylbenzene sulfonates and the C₁₃ -C₁₇ paraffinor alkane sulfonates. Particularly, preferred compounds are sodium C₁₀-C₁₃ alkylbenzene sulfonate and sodium C₁₃ -C₁₇ alkane sulfonate.

Generally, the proportion of the nonsoap-anionic surfactant will be inthe range of 0.1% to 20.0%, preferably from 1% to 7%, by weight of thedilute o/w microemulsion composition or the all purpose hard surfacecleaning composition.

The instant composition contains a composition (herein after referred toas an ethoxylated polyhydric alcohol type compound such as anethoxylated glycerol type compound) which is a mixture of a fullyesterified ethoxylated polyhydric alcohol, a partially esterifiedethoxylated polyhydric alcohol and a nonesterified ethoxylatedpolyhydric alcohol, wherein the preferred polyhydric alcohol isglycerol, and the compound is ##STR3## wherein w equals one to four,most preferably one, and B is selected from the group consisting ofhydrogen or a group represented by: ##STR4## wherein R is selected fromthe group consisting of alkyl group having 6 to 22 carbon atoms, morepreferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22carbon atoms, more preferably 11 to 15 carbon atoms, wherein ahydrogenated tallow alkyl chain or a coco alkyl chain is most preferred,wherein at least one of the B groups is represented by said ##STR5## andR' is selected from the group consisting of hydrogen and methyl groups;x, y and z have a value between 0 and 60, more preferably 0 to 40,provided that (x+y+z) equals 2 to 100, preferably 4 to 24 and mostpreferably 4 to 19, wherein in Formula (I) the weight ratio ofmonoester/diester/triester is 40 to 90/5 to 35/1 to 20, more preferably50 to 90/9 to 32/1 to 12, wherein the weight ratio of Formula (I) toFormula (II) is a value between 3 to 0.02, preferably 3 to 0.1, mostpreferably 1.5 to 0.2, wherein it is most preferred that there is moreof Formula (II) than Formula (I) in the mixture that forms the compound.

The ethoxylated glycerol type compound used in the instant compositionis manufactured by the Kao Corporation and sold under the trade nameLevenol such as Levenol F-200 which has an average EO of 6 and a molarratio of coco fatty acid to glycerol of 0.55 or Levenol V501/2 which hasan average EO of 17 and a molar ratio of tallow fatty acid to glycerolof 1.0. It is preferred that the molar ratio of the fatty acid toglycerol is less than 1.7, more preferably less than 1.5 and mostpreferably less than 1.0. The ethoxylated glycerol type compound has amolecular weight of 400 to 1600, and a pH (50 grams / liter of water) of5-7. The Levenol compounds are substantially non irritant to human skinand have a primary biodegradabillity higher than 90% as measured by theWickbold method Bias-7d.

Two examples of the Levenol compounds are Levenol V-501/2 which has 17ethoxylated groups and is derived from tallow fatty acid with a fattyacid to glycerol ratio of 1.0 and a molecular weight of 1465 and LevenolF-200 has 6 ethoxylated groups and is derived from coco fatty acid witha fatty acid to glycerol ratio of 0.55. Both Levenol F-200 and LevenolV-501/2 are composed of a mixture of Formula (I) and Formula (II). TheLevenol compounds has ecoxicity values of algae growth inhibition >100mg/liter; acute toxicity for Daphniae >100 mg/liter and acute fishtoxicity >100 mg/liter. The Levenol compounds have a readybiodegradability higher than 60% which is the minimum required valueaccording to OECD 301 B measurement to be acceptably biodegradable.

Polyesterified nonionic compounds also useful in the instantcompositions are Crovol PK-40 and Crovol PK-70 manufactured by CrodaGMBH of the Netherlands. Crovol PK-40 is a polyoxyethylene (12) PalmKernel Glyceride which has 12 EO groups. Crovol PK-70 which is preferedis a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups.

In the dilute microemulsion compositions or the all purpose hard surfacecleaning compositions the ethoxylated polyhydric alcohol compounds orthe polyesterified nonionic compounds will be present in admixture withthe anionic surfactant. The proportion of the ethoxylated polyhydricalcohol compound based upon the weight of the all purpose hard surfacecleaning composition or the final dilute microemulsion composition willbe 0.1% to 10%, more preferably 0.5% to 10%, most preferably 0.5% to 6%by weight.

In the more preferred compositions the weight ratio of nonsoap anionicsurfactant to the ethoxylated polyhydric alcohol compound will be in therange of 3:1 to 1:3 with especially good results being obtained at aweight ratio of 2:1.

The grease release system of the instant composition comprises a mixturethe compound which is the mixture of the fully esterified ethoxylatedpolyhydric alcohol, the partially esterified ethoxylated polyhydricalcohol and the nonesterified ethoxylated polyhydric alcohol andoptionally a supplemental grease release agent. One of the supplementalgrease release agent of the instant invention which can be used in thegrease release system is characterized by the formula: ##STR6## whereinR₁ is a methyl group and R₂, R₃ and R₄ are independently selected fromthe group consisting of methyl, ethyl and CH₂ CH₂ Y, wherein Y isselected from the group consisting of Cl, Br, CO₂ H, (CH₂ O)n OH whereinn=1 to 10, OH, CH₂ CH₂ OH and X⁻ is selected from the group consistingof Cl, Br, methosulfate ##STR7## Preferred supplemental grease releaseagents are Beta-hydroxyethyltrimethyl ammonium chloride (cholinechloride), Beta-chloroethyltrimethyl ammonium chloride, andtri(Beta-hydroxyethyl) methyl ammonium methosulfate (Stepanquat T),wherein the choline chloride is preferred.

It is theorized that the positively charged grease release agent iselectrostatically bonded to the negatively charged groups on the surfaceof the surface to be cleaned such as a ceramic thereby preventingbonding of calcium ions contained in grease to the negative chargedsurface of the ceramic tile. The concentration of the grease releaseagent in the instant microemulsion composition is 0 to 10 wt. %, morepreferably 0.1 wt. % to 10 wt. % and most preferably 0.5 wt. % to 8.0wt. %.

The supplemental grease release agents of the present invention can alsobe the anionic surfactant of the instant compositions being associatedin the composition with a polyethylene glycol having a molecular weightof 500 to 1,000, wherein the polyethylene glycol has the structure

    HO(CH.sub.2 CH.sub.2 O).sub.n H

wherein n is 11 to 52. The concentration of the polyethylene glycol inthe instant composition is 0 to 10.0 wt. %, more preferably 0.1 wt. %to10 wt. %, and most preferably 0.5 wt. % to 8.0 wt. %, wherein the ratioof anionic surfactant to the polyethylene glycol is 5:1 to 1:5.

Another class of supplemental grease release agents which can be used inthe grease release system of the present invention are an ethoxylatedmaleic anhydride-alpha-olefin copolymer having a comblike structure withboth hydrophobic and hydrophilic chains. The polymer is made by AkzoChemie America and has a number average molecular weight of 10,000 to30,000, most preferably 15,000 to 25,000. The ethoxylated maleicanhydride-alpha-olefin copolymer which is used at a concentration of 0.5to 10.0 wt. % more preferably 1.0 to 8.0 wt. %, is depicted by theformula: ##STR8## wherein n is 5 to 14, preferably 7 to 9, x is 7 to 19,preferably 8 to 19 w and z can each be 5 wt. % to 95 wt. % and y is ofsuch a value as to provide a molecular weight 10,000 to 30,000.

Another class of grease release agents manufactured by BASF that areused in the grease release system of the present invention at aconcentration of 0 to 10 wt. %, ore preferably 0.5 to 8.0 wt. %, is apolymer depicted by the formula: ##STR9## wherein x is hydrogen or analkali metal cation such as potassium sodium and n is a number from 2 to16, preferably 2 to 10, R₁ is selected from the group consisting ofmethyl or hydrogen, R₂ is a C₁ to C₁₂, preferably C₄ to C₈, linear orbranched chained alkyl group and R₃ is a C₂ to C₁₆, preferably C₂ to C₁₂linear or branched chained alkyl group and y is of such a value as toprovide a molecular weight of about 5,000 to about 15,000.

Compounds found to provide highly suitable cosurfactants for themicroemulsion over temperature ranges extending from 5° C. to 43° C. forinstance are glycerol, ethylene glycol, water-soluble polyethyleneglycols having a molecular weight of 300 to 1000, polypropylene glycolof the formula HO(CH₃ CHCH₂ O)_(n) H wherein n is a number from 2 to 18,mixtures of polyethylene glycol and polypropyl glycol (Synalox) and monoC₁ -C₆ alkyl ethers and esters of ethylene glycol and propylene glycolhaving the structural formulas R(X)_(n) OH and R₁ (X)_(n) OH wherein Ris C₁ -C₆ alkyl group, R₁ is C₂ -C₄ acyl group, X is (OCH₂ CH₂) or (OCH₂(CH₃)CH) and n is a number from 1 to 4, diethylene glycol, triethyleneglycol, an alkyl lactate, wherein the alkyl group has 1 to 6 carbonatoms, 1 methoxy-2-propanol, 1methoxy-3-propanol, and 1 methoxy 2-, 3-or 4-butanol, (2) aliphatic mono- and di-carboxylic acids containing 2to 10 carbon atoms, preferably 3 to 6 carbons in the molecule; and (3)triethyl phosphate. Additionally, mixtures of two or more of the threeclasses of cosurfactant compounds may be employed where specific pH'sare desired.

When the mono- and di-carboxylic acid (Class 2) cosurfactants areemployed in the instant microemulsion compositions at a concentration of2 to 10 wt. %, the microemulsion compositions can be used as a cleanersfor bathtubs and other hard surfaced items, which are acid resistantthereby removing lime scale, soap scum and greasy soil from the surfacesof such items damaging such surfaces. If these surfaces are of zirconiumwhite enamel, they can be damaged by these compositions.

An aminoalkylene phophoric acid at a concentration of 0.01 to 0.2 wt. %can be optionally used in conjunction with the mono- and di-carboxylicacids, wherein the aminoalkylene phosphoric acid helps prevent damage tozirconium white enamel surfaces. Additionally, 0.05 to 1% of phosphoricacid can be used in the composition.

Representative members of the aliphatic carboxylic acids include C₃ -C₆alkyl and alkenyl monobasic acids such as acrylic acid and propionicacid and dibasic acids such as glutaric acid and mixtures of glutaricacid with adipic acid and succinic acid, as well as mixtures of theforegoing acids.

While all of the aforementioned glycol ether compounds and acidcompounds provide the described stability, the most preferredcosurfactant compounds of each type, on the basis of cost and cosmeticappearance (particularly odor), are diethylene glycol monobutyl etherand a mixture of adipic, glutaric and succinic acids, respectively. Theratio of acids in the foregoing mixture is not particularly critical andcan be modified to provide the desired odor. Generally, to maximizewater solubility of the acid mixture glutaric acid, the mostwater-soluble of these three saturated aliphatic dibasic acids, will beused as the major component.

Generally, weight ratios of adipic acid:glutaric acid:succinic acid is1-3:1-8:1-5, preferably 1-2:1-6:1-3, such as 1:1:1, 1:2:1, 2:2:1,1:2:1.5, 1:2:2, 2:3:2, etc. can be used with equally good results.

Representative members of the polypropylene glycol include dipropyleneglycol and polypropylene glycol having a molecular weight of 200 to1000, e.g., polypropylene glycol 400. Other satisfactory glycol ethersare ethylene glycol monobutyl ether (butyl cellosolve), diethyleneglycol monobutyl ether (butyl carbitol), triethylene glycol monobutylether, mono, di, tri propylene glycol monobutyl ether, tetraethyleneglycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether,propylene glycol monomethyl ether, ethylene glycol monohexyl ether,diethylene glycol monohexyl ether, propylene glycol tertiary butylether, ethylene glycol monoethyl ether, ethylene glycol monomethylether, ethylene glycol monopropyl ether, ethylene glycol monopentylether, diethylene glycol monomethyl ether, diethylene glycol monoethylether, diethylene glycol monopropyl ether, diethylene glycol monopentylether, triethylene glycol monomethyl ether, triethylene glycol monoethylether, triethylene glycol monopropyl ether, triethylene glycolmonopentyl ether, triethylene glycol monohexyl ether, mono, di,tripropylene glycol monoethyl ether, mono, di tripropylene glycolmonopropyl ether, mono, di, tripropylene glycol monopentyl ether, mono,di, tripropylene glycol monohexyl ether, mono, di, tributylene glycolmono methyl ether, mono, di, tributylene glycol monoethyl ether, mono,di, tributylene glycol monopropyl ether, mono, di, tributylene glycolmonobutyl ether, mono, di, tributylene glycol monopentyl ether and mono,di, tributylene glycol monohexyl ether, ethylene glycol monoacetate anddipropylene glycol propionate.

Still other classes of cosurfactant compounds providing stablemicroemulsion compositions at low and elevated temperatures are themono-, di- and triethyl esters of phosphoric acid such as triethylphosphate.

The amount of cosurfactant required to stabilize the microemulsioncompositions will, of course, depend on such factors as the surfacetension characteristics of the cosurfactant, the type and amounts of theprimary surfactants and perfumes, and the type and amounts of any otheradditional ingredients which may be present in the composition and whichhave an influence on the thermodynamic factors enumerated above.Generally, amounts of cosurfactant used in the microemulsion is in therange of from 0.1% to 50%, preferably from 0.5% to 15%, especiallypreferably from 1% to 7%, by weight provide stable dilute o/wmicroemulsions for the above-described levels of primary surfactants andperfume and any other additional ingredients as described below. Theamount of cosurfactant in the all purpose hard surface cleaningcomposition will be in the range of 0 to 50%, more preferably 0.1% to50%, most preferably 0.5% to 15% by weight.

As will be appreciated by the practitioner, the pH of the finalmicroemulsion will be dependent upon the identity of the cosurfactantcompound, with the choice of the cosurfactant being effected by cost andcosmetic properties, particularly odor. For example, microemulsioncompositions which have a pH in the range of 1 to 10 may employ eitherthe class 1 or the class 4 cosurfactant as the sole cosurfactant, butthe pH range is reduced to 1 to 8.5 when the polyvalent metal salt ispresent. On the other hand, the class 2 cosurfactant can only be used asthe sole cosurfactant where the product pH is below 3.2. However, wherethe acidic cosurfactants are employed in admixture with a glycol ethercosurfactant, compositions can be formulated at a substantially neutralpH (e.g., pH 7±1.5, preferably 7±0.2).

The ability to formulate neutral and acidic products without builderswhich have grease removal capacities is a feature of the presentinvention because the prior art o/w microemulsion formulations mostusually are highly alkaline or highly built or both.

In addition to their excellent capacity for cleaning greasy and oilysoils, the low pH microemulsion formulations also exhibit excellentcleaning performance and removal of soap scum and lime scale in neat(undiluted) as well as in diluted usage.

The final essential ingredient in the inventive microemulsioncompositions having improved interfacial tension properties is water.The proportion of water in the microemulsion or all purpose hard surfacecleaning composition compositions generally is in the range of 20% to97%, preferably 70% to 97% by weight.

As believed to have been made clear from the foregoing description, thedilute o/w microemulsion liquid all-purpose cleaning compositions ofthis invention are especially effective when used as is, that is,without further dilution in water, since the properties of thecomposition as an o/w microemulsion are best manifested in the neat(undiluted) form. However, at the same time it should be understood thatdepending on the levels of surfactants, cosurfactants, perfume and otheringredients, some degree of dilution without disrupting themicroemulsion, per se, is possible. For example, at the preferred lowlevels of active surfactant compounds (i.e., primary anionic andnonionic detergents) dilutions up to 50% will generally be welltolerated without causing phase separation, that is, the microemulsionstate will be maintained.

However, even when diluted to a great extent, such as a 2- to 10-fold ormore dilution, for example, the resulting compositions are stilleffective in cleaning greasy, oily and other types of soil. Furthermore,the presence of magnesium ions or other polyvalent ions, e.g., aluminum,as will be described in greater detail below further serves to boostcleaning performance of the primary detergents in dilute usage.

On the other hand, it is also within the scope of this invention toformulate highly concentrated microemulsions which will be diluted withadditional water before use.

The present invention also relates to a stable concentratedmicroemulsion or acidic microemulsion composition comprisingapproximately by weight:

(a) 0.1 to 30% of an anionic surfactant;

(b) 0.1 to 10% of an ethoxylated polyhydric alcohol type compound;

(c) 0.1 to 50% of a cosurfactant;

(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;

(e) 0 to 18% of at least one dicarboxylic acid;

(f) 0 to 1% of phosphoric acid;

(g) 0 to 0.2% of an aminoalkylene phosphoric acid;

(h) 0 to 15% of magnesium sulfate heptahydrate;

(i) 0 to 10%, more preferably 0.1% to 10% of a supplemental greaserelease agent and;

(j) balance being water, wherein the composition has an ecotoxocity asmeasured by the LC 50 test of at least 0.18 ml/L measured on Daphniaemicroorganisms.

Such concentrated microemulsions can be diluted by mixing with up to 20times or more, preferably 4 to 10 times their weight of water to formo/w microemulsions similar to the diluted microemulsion compositionsdescribed above. While the degree of dilution is suitably chosen toyield an o/w microemulsion composition after dilution, it should berecognized that during the course of dilution both microemulsion andnon-microemulsions may be successively encountered.

In addition to the above-described essential ingredients required forthe formation of the microemulsion composition, the compositions of thisinvention may often and preferably do contain one or more additionalingredients which serve to improve overall product performance.

One such ingredient is an inorganic or organic salt of oxide of amultivalent metal cation, particularly Mg⁺⁺. The metal salt or oxideprovides several benefits including improved cleaning performance indilute usage, particularly in soft water areas, and minimized amounts ofperfume required to obtain the microemulsion state. Magnesium sulfate,either anhydrous or hydrated (e.g., heptahydrate), is especiallypreferred as the magnesium salt. Good results also have been obtainedwith magnesium oxide, magnesium chloride, magnesium acetate, magnesiumpropionate and magnesium hydroxide. These magnesium salts can be usedwith formulations at neutral or acidic pH since magnesium hydroxide willnot precipitate at these pH levels.

Although magnesium is the preferred multivalent metal from which thesalts (inclusive of the oxide and hydroxide) are formed, otherpolyvalent metal ions also can be used provided that their salts arenontoxic and are soluble in the aqueous phase of the system at thedesired pH level.

Thus, depending on such factors as the pH of the system, the nature ofthe primary surfactants and cosurfactant, and so on, as well as theavailability and cost factors, other suitable polyvalent metal ionsinclude aluminum, copper, nickel, iron, calcium, etc. It should benoted, for example, that with the preferred paraffin sulfonate anionicdetergent calcium salts will precipitate and should not be used. It hasalso been found that the aluminum salts work best at pH below 5 or whena low level, for example 1 weight percent, of citric acid is added tothe composition which is designed to have a neutral pH. Alternatively,the aluminum salt can be directly added as the citrate in such case. Asthe salt, the same general classes of anions as mentioned for themagnesium salts can be used, such as halide (e.g., bromide, chloride),sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.

Preferably, in the dilute compositions the metal compound is added tothe composition in an amount sufficient to provide at least astoichiometric equivalent between the anionic surfactant and themultivalent metal cation. For example, for each gram-ion of Mg++ therewill be 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate,etc., while for each gram-ion of A1³⁺ there will be 3 gram moles ofanionic surfactant. Thus, the proportion of the multivalent saltgenerally will be selected so that one equivalent of compound willneutralize from 0.1 to 1.5 equivalents, preferably 0.9 to 1.4equivalents, of the acid form of the anionic surfactant. At higherconcentrations of anionic surfactant, the amount of multivalent saltwill be in range of 0.5 to 1 equivalents per equivalent of anionicsurfactant.

The o/w microemulsion compositions will include from 0% to 2.5%,preferably from 0.1% to 2.0% by weight of the composition of a C₈ -C₂₂fatty acid or fatty acid soap as a foam suppressant.

The addition of fatty acid or fatty acid soap provides an improvement inthe rinseability of the composition whether applied in neat or dilutedform. Generally, however, it is necessary to increase the level ofcosurfactant to maintain product stability when the fatty acid or soapis present if more than 2.5 wt. % of a fatty acid is used in the instantcompositions, the composition will become unstable at low temperaturesas well as having an objectionable smell.

As example of the fatty acids which can be used as such or in the formof soap, mention can be made of distilled coconut oil fatty acids,"mixed vegetable" type fatty acids (e.g. high percent of saturated,mono-and/or polyunsaturated C₁₈ chains); oleic acid, stearic acid,palmitic acid, eiocosanoic acid, and the like, generally those fattyacids having from 8 to 22 carbon atoms being acceptable.

The all-purpose liquid cleaning composition of this invention may, ifdesired, also contain other components either to provide additionaleffect or to make the product more attractive to the consumer. Thefollowing are mentioned by way of example: Colors or dyes in amounts upto 0.5% by weight; bactericides in amounts up to 1% by weight;preservatives or antioxidizing agents, such as formalin,5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one,2,6-di-tert. butyl-p-cresol, etc., in amounts up to 2% by weight; and pHadjusting agents, such as sulfuric acid or sodium hydroxide, as needed.Furthermore, if opaque compositions are desired, up to 4% by weight ofan opacifier may be added.

In final form, the all-purpose hard surface liquid cleaning compositionsand clear microemulsions exhibit stability at reduced and increasedtemperatures. More specifically, such compositions remain clear andstable in the range of 5° C. to 50° C., especially 10° C. to 43° C. Suchcompositions exhibit a pH in the acid or neutral range depending onintended end use. The liquids are readily pourable and exhibit aviscosity in the range of 6 to 60 milliPascal . second (mPas.) asmeasured at 25° C. with a Brookfield RVT Viscometer using a #1 spindlerotating at 20 RPM. Preferably, the viscosity is maintained in the rangeof 10 to 40 mPas.

The compositions are directly ready for use or can be diluted as desiredand in either case no or only minimal rinsing is required andsubstantially no residue or streaks are left behind. Furthermore,because the compositions are free of detergent builders such as alkalimetal polyphosphates they are environmentally acceptable and provide abetter "shine" on cleaned hard surfaces.

When intended for use in the neat form, the liquid compositions can bepackaged under pressure in an aerosol container or in a pump-typesprayer for the so-called spray-and-wipe type of application.

Because the compositions as prepared are aqueous liquid formulations andsince no particular mixing is required to form the o/w microemulsion,the compositions are easily prepared simply by combining all theingredients in a suitable vessel or container. The order of mixing theingredients is not particularly important and generally the variousingredients can be added sequentially or all at once or in the form ofaqueous solutions of each or all of the primary detergents andcosurfactants can be separately prepared and combined with each otherand with the perfume. The magnesium salt, or other multivalent metalcompound, when present, can be added as an aqueous solution thereof orcan be added directly. It is not necessary to use elevated temperaturesin the formation step and room temperature is sufficient.

The instant microemulsion formulas explicitly exclude alkali metalsilicates and alkali metal builders such as alkali metal polyphosphates,alkali metal carbonates, alkali metal phosphonates and alkali metalcitrates because these materials, if used in the instant composition,would cause the composition to have a high pH as well as leaving residueon the surface being cleaned.

It is contemplated within the scope of the instant invention that theinstant partially esterified ethoxylated polyhydric alcohol compound canbe employed in hard surface cleaning compositions such as wood cleaners,window cleaners and light duty liquid cleaners.

The following examples illustrate liquid cleaning compositions of thedescribed invention. Unless otherwise specified, all percentages are byweight. The exemplified compositions are illustrative only and do notlimit the scope of the invention. Unless otherwise specified, theproportions in the examples and elsewhere in the specification are byweight.

EXAMPLE 1

The following compositions in wt. % were prepared by simple mixing at25° C.:

    __________________________________________________________________________                                  Mr.   St Marc                                             A   B   C   D   E   Proper                                                                              Lemon                                     __________________________________________________________________________    Sodium C.sub.13 -C.sub.17                                                               4.7 4.3 4   4.3 4.7 2.9   --                                        Paraffin sulfonate                                                            EO/PO nonionic                                                                          --  --  --  --      --    3.2                                       Levenol F-200                                                                           2.3 2.2 2   2.2 2.3 --    --                                        C.sub.13 -C.sub.5 EO 14                                                                 --  --  --  --      3.3   --                                        nonionic                                                                      DEGMBE    4   4   3.5 4   4.0 4.4   3                                         Coco fatty acid                                                                         0.75                                                                              0.5 0.4 0.75                                                                              0.5 0.65  0.3                                       Lauric acid               0.25                                                choline chloride          4.0                                                 MgSO.sub.4 7H.sub.2 O                                                                   2.2 2   1.9 2.2 2.1 --    --                                        Perfume (a)                                                                             0.8 0.75                                                                              0.9 0.7 0.8 present                                                                             present                                   Sodium Citrate                                                                          --  --  --  --      3.2   --                                        Water + Minors                                                                          Bal Bal Bal Bal Bal Bal   Bal                                       pH        7   7   7   7   7   9.5   7                                         Degreasing test                                                               Neat (b)  30  35  35  35  30  70    >100                                      Dilute (b)                                                                              45  60  60  60  45  >90   90                                        Residue   Equal                                                                             Equal                                                                             Equal                                                                             Equal                                                                             Equal                                                                             Worse Equal to ref.                                       to ref.                                                                           to ref.                                                                           to ref.                                                                           to ref.                                                                           to ret                                                        (d)                                                                 Foam in hard Water                                                                      Equal                                                                             Equal                                                                             Equal                                                                             Equal                                                                             Equal                                                                             Equal to ref.                                                                       Equal to ref.                                       to ref.                                                                           to ref.                                                                           to ref.                                                                           to ref.                                                                           to ref                                              LC50-Ecotoxicity on                                                                     0.18                                                                              --  --  --      0.1 ml/l                                                                            0.033 ml/l                                Daphniae (c)                                                                            ml/l                                                                __________________________________________________________________________     (a) contains 25% by weight of terpenes.                                       (b) the lower the number of strokes, the better the degreasing                performance.                                                                  (c) the higher the results, the lower the ecotoxicity.                        (d) reference compounds is Example I of U.S. Pat. No. 5,108,643.         

Furthermore, "dissolution power" of the o/w microemulsion of thisexample is compared to the "dissolution power" of an identicalcomposition except that an equal amount (5 weight percent) of sodiumcumene sulfonate hydrotrope is used in place of the diethylene glycolmonobutyl ether cosurfactant in a test wherein equal concentrations ofheptane are added to both compositions. The o/w microemulsion of thisinvention solubilizes 12 grams of the water immiscible substance ascompared to 1.4 grams in the hydrotrope containing liquid composition.

In a further comparative test using blue colored cooking oil - - - afatty triglyceride soil - - -, the composition of Example 1 is clearafter the addition of 0.2 grams of cooking oil whereas the cooking oilfloats on the top of the composition containing the sulfonatehydrotrope.

When the concentration of perfume is reduced to 0.4% in the compositionof Example 1, a stable o/w microemulsion composition is obtained.Similarly, a stable o/w microemulsion is obtained when the concentrationof perfume is increased to 2% by weight and the concentration ofcosurfactant is increased to 6% by weight in Example 1.

EXAMPLE 2

The example illustrates a typical formulation of a "concentrated" o/wmicroemulsion based on the present invention:

    ______________________________________                                                          % by weight                                                 ______________________________________                                        Coco fatty acid     5                                                         Sodium C.sub.13 -C.sub.17 Paraffin Sulfonate                                                      25                                                        Levenol F-200       14.5                                                      diethylene glycol monobutyl ether                                                                 20                                                        Perfume (a)         15                                                        Water               Bal to 100                                                pH: 7.0 ± 0.2                                                              ______________________________________                                    

This concentrated formulation can be easily diluted, for example, fivetimes with tap water, to yield a diluted o/w microemulsion composition.Thus, by using microemulsion technology it becomes possible to provide aproduct having high levels of active detergent ingredients and perfume,which has high consumer appeal in terms of clarity, odor and stability,and which is easily diluted at the usual usage concentration for similarall-purpose hard surface liquid cleaning compositions, while retainingits cosmetically attractive attributes.

EXAMPLE 3

This example illustrates a diluted o/w microemulsion compositionaccording to the invention having an acidic pH and which also providesimproved cleaning performance on soap scum and lime scale removal aswell as for cleaning greasy soil.

    ______________________________________                                                                % by weight                                           ______________________________________                                        Coco fatty acid           0.75                                                Sodium C.sub.13 -C.sub.17 paraffin sulfonate                                                            4.7                                                 Levenol F-200             2.3                                                 Mg SO.sub.4 7H.sub.2 O    2.2                                                 Mixture of succinic acid/glutaric acid/adipic acid (1:1:1)                                              5                                                   Perfume (d)               1.0                                                 Water, minors (dye)       balance to 100                                      Phosphoric acid           0.2                                                 Amino tris - (methylene-phosphonic acid)                                                                0.03                                                pH = 3 ± 0.2                                                               ______________________________________                                         (d) contains 40% by weight of terpene                                    

EXAMPLE 4

Formula A of Example 1 was tested for the removal of a combination ofgrease and particulate soil as well as for a grease release effect andcompared to commercial Ajax™NME

I. Grease+particulate soil removal;

Test Method

A) Soil composition:

70 g of mineral oil

35 g of particulate soil (vacuum cleaner dust+1% of carbon black)

35 g C₂ Cl₄

B) Soil preparation:

Weigh cleaned/dried glass tiles

Soil the tiles with the grease+particulate soil

Bake the tiles 1 hour at 80° C.

Weigh the soiled tiles which aged 2 hours at RT.

C) Soil removal:

The soiled tiles are soaked for 15 minutes at RT in the test products,then they are delicately rinsed with tap water. After drying 45 minutesat 50° C., the tiles are weighed again.

    ______________________________________                                        Results                                                                                      Grease + particulate soil                                                     % of removal                                                                  mean of 6 tiles                                                ______________________________________                                        Commercial Ajax ™ NME                                                                       60                                                           Formula A of Example I                                                                         95                                                           ______________________________________                                    

Formula A exhibits improved grease+particulate soil removal over theCommercial Ajax™NME

II. Grease release effect

Test Method

A) Soil composition:

20% hardened tallow

80% beef tallow

fat blue dye

B) Soil preparation:

The fat mixture is heated and sprayed with an automatic spraying deviceon cleaned and dried ceramic tiles.

C) Soil removal:

Product used neat: 2.5 g on sponge

Product used dilute: 1.2% sol in tap water--10 ml of the solution on thesponge

The cleaning procedure is done with the gardner device for both productconcentrations.

Results

A) On treated ceramic tiles (treated with the product before sprayingthe soil)

    ______________________________________                                                           Neat   Dilute                                                                Number of Strokes                                           ______________________________________                                                             mean of 4                                                                              mean of 6                                       First grease layer deposition                                                                      tiles    tiles                                           ______________________________________                                        Commercial Current Ajax ™ NME                                                                   27       19                                              Formula A            19        5*                                             ______________________________________                                        Second grease layer deposition on the                                                              mean of 4                                                                              mean of 6                                       same tile            tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           25       48                                              Formula A            25        18*                                            ______________________________________                                    

B) On untreated ceramic tiles

In addition to the previous test, the 3 following procedures were usedto verify that Formula A remains on the surface after rinsing or wiping.After the first cleaning procedure and before the second spraying:

1) the tiles were allowed to dry in open air

2) the surface was wiped with paper towel

3) the surface was rinsed with wet sponge

1) dry in open air

    ______________________________________                                                           Neat   Dilute                                                                Number of Strokes                                           ______________________________________                                                             mean of 4                                                                              mean of 6                                       First grease layer deposition                                                                      tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           29       30                                              Formula A            27       32                                              ______________________________________                                        Second grease layer deposition on the                                                              mean of 4                                                                              mean of 6                                       same tile            tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           33       21                                              Formula A            30        6*                                             ______________________________________                                    

2) wipe dry the surface

    ______________________________________                                                           Neat   Dilute                                                                Number of Strokes                                           ______________________________________                                                             mean of 4                                                                              mean of 6                                       First grease layer deposition                                                                      tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           29       30                                              Formula A            27       32                                              ______________________________________                                        Second grease layer deposition on the                                                              mean of 4                                                                              mean of 6                                       same tile            tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           35       46                                              Formula A            30         48.5                                          ______________________________________                                    

3) wet wiping the surface

    ______________________________________                                                           Neat   Dilute                                                                Number of Strokes                                           ______________________________________                                                             mean of 4                                                                              mean of 6                                       First grease layer deposition                                                                      tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           29       30                                              Formula A            27       32                                              ______________________________________                                        Second grease layer deposition on the                                                              mean of 4                                                                              mean of 6                                       same tile            tiles    tiles                                           ______________________________________                                        Commercial Ajax ™ NME                                                                           34       58                                              Formula A            27        41**                                           ______________________________________                                         *highly significant difference                                                **after 5 strokes, 65% of the grease is already removed                  

These results clearly demonstrate the important grease release effectobtained with Formula A especially when the product is used dilute.

Formula 1-E of example 1 was tested for grease release. The combinationof Levenol plus Choline chloride provides a superior grease releaseeffect to the microemulsion composition.

1.a. Treated with the neat product; drying in open air before sprayingthe soil

    ______________________________________                                                   number of                                                                     strokes for                                                                           number of strokes for second                                          first cleaning                                                                        cleaning after drying in open air                          ______________________________________                                        Formula 1-E  24        23                                                     current AJAX ™ NME                                                                      46        40                                                     ______________________________________                                    

1.a. Treated with the neat product; wiping with wet sponges beforespraying the soil

    ______________________________________                                                   number of                                                                     strokes for                                                                           number of strokes for second                                          first cleaning                                                                        cleaning after drying in open air                          ______________________________________                                        Formula 1-E  32        19                                                     current AJAX ™ NME                                                                      53        27                                                     ______________________________________                                    

1.a. Treated with the diluted product; drying in open air beforespraying the soil

    ______________________________________                                                   number of                                                                     strokes for                                                                           number of strokes for second                                          first cleaning                                                                        cleaning after drying in open air                          ______________________________________                                        Formula 1-E   3         2                                                     current AJAX ™ NME                                                                      18        19                                                     ______________________________________                                    

1.a. Treated with the diluted product; wiping with wet sponges beforespraying the soil

    ______________________________________                                                   number of                                                                     strokes for                                                                           number of strokes for second                                          first cleaning                                                                        cleaning after drying in open air                          ______________________________________                                        Formula 1-E   9        12                                                     current AJAX ™ NME                                                                      20        21                                                     ______________________________________                                    

2. Non pretreated tiles

Cleaning with diluted products.

    ______________________________________                                                              number of strokes for                                              number of strokes                                                                        second cleaning after                                              for first cleaning                                                                       drying in open air                                      ______________________________________                                        Formula 1-E  27           3                                                   current AJAX.sup.tm NME                                                                    30           14                                                  ______________________________________                                    

In summary, the described invention broadly relates to an improvement inmicroemulsion and all purpose hard surface cleaning compositionscontaining an anionic surfactant, a partially esterified ethoxylatedpolyhydric alcohol, optionally a supplemental grease release agent, oneof the specified cosurfactants, a hydrocarbon ingredient and water.

What is claimed:
 1. A micro emulsion composition comprising:(a) 0.1 wt.% to 20 wt. % of a nonsoap anionic surfactant; (b) 0.1 wt. % to 10 wt. %of a mixture of ##STR10## wherein w equals one to four, and B isselected from the group consisting of hydrogen and a group representedby: ##STR11## wherein R is selected from the group consisting of alkylgroup having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22carbon atoms, wherein at least one of the B groups is represented bysaid ##STR12## R' is selected from the group consisting of hydrogen andmethyl groups; x, y and z have a value between 0 and 60, provided that(x+y+z) equals 2 to 100, wherein in Formula (I) the weight ratio ofmonoester/diester/triester is 40 to 90/5 to 35/1 to 20, wherein theweight ratio of Formula (I) and Formula (II) is a value between 3 and0.02; (c) 0 to 10 wt. % of a grease release agent wherein said greaserelease agent is characterized by the formula ##STR13## wherein R₁ is amethyl group and R₂, R₃ and R₄ are independently selected from the groupconsisting of methyl, ethyl and CH₂ CH₂ Y, where Y is selected from thegroup consisting of Cl, Br, CO₂ H, (CH₂ O)_(n) OH wherein n=1 to 10, OH,CH₂ CH₂ OH and X⁻ is selected from the group consisting of Cl, Br,methosulfate ##STR14## wherein said grease release agent is apolyethylene glycol complexed with said anionic surfactant and saidpolyethylene glycol has a molecular weight of 500 to 1,000, wherein thepolyethylene glycol has the structure

    HO(CH.sub.2 CH.sub.2 O).sub.n H

wherein n is 11 to 52, or wherein said grease release agent is depictedby the formula: ##STR15## wherein n is 5 to 14, x is 7 to 19, w and zcan each be 5 wt. % to 95 wt. % and y is of such a value as to provide amolecular weight 10,000 to 30,000, or wherein said grease release agentis depicted by the formula: ##STR16## wherein x is hydrogen or an alkalimetal cation and n is a number from 2 to 16, R₁ is selected from thegroup consisting of methyl and hydrogen, R₂ is a C₁ to C₁₂, linear orbranched chain alkyl group and R₃ is a C₂ to C₁₆, linear or branchedchain alkyl group and y is of such a value as to provide a molecularweight of about 5,000 to about 15,000; (d) 0.1 wt. % to 50 wt. % of awater soluble glycol ether or a C3-C6 aliphatic carboxylic acidcosurfactant; (e) 0.1 wt. % to 10 wt. % of a water insolublehydrocarbon, essential off or a perfume; and (f) the balance beingwater.
 2. The microemulsion composition of claim 1 which furthercontains a salt of a multivalent metal cation in an amount sufficient toprovide from 0.5 to 1.5 equivalents of said cation per equivalent ofsaid anionic surfactant.
 3. The microemulsion composition of claim 2wherein said salt of the multivalent metal cation is magnesium oraluminum.
 4. The microemulsion composition of claim 2, wherein saidcomposition contains 0.9 to 1.4 equivalents of said cation perequivalent of anionic surfactant.
 5. The microemulsion composition ofclaim 3 wherein said multivalent salt is magnesium oxide or magnesiumsulfate.
 6. The microemulsion composition of claim 1 which contains from0.5 to 15% by weight of said cosurfactant and from 0.4% to 3.0% byweight of said hydrocarbon.
 7. The microemulsion composition of claim 1wherein glycol ether is selected from the group consisting of ethyleneglycol monobutylether, diethylene glycol monobutyl ether, triethyleneglycol monobutylether, and propylene glycol tert.butyl ether, and mono-,di-, and tri-propylene glycol monobutyl ether.
 8. The microemulsioncomposition of claim 1 wherein the glycol ether is ethylene glycolmonobutyl ether or diethylene glycol monobutyl ether.
 9. Themicroemulsion composition of claim 1 wherein the cosurfactant is said C₃-C₆ aliphatic carboxylic acid selected from the group consisting ofacrylic acid, propionic acid, glutaric acid, mixtures of glutaric addand succinic acid and adipic acid, and mixtures of any of the foregoing.10. The microemulsion composition of claim 9 wherein the aliphaticcarboxylic acid is a mixture of adipic acid, glutaric acid and succinicacid.
 11. The microemulsion composition of claim 1 wherein the anionicsurfactant is a C₉ -C₁₅ alkyl benzene sulfonate or a C₁₀ -C₂₀ alkanesulfonate.
 12. The microemulsion composition of claim 1 wherein saidgrease release agent is present at a concentration of about 0.1 wt. % toabout 10.0 wt. %.
 13. An all purpose hard surface cleaning compositioncomprising approximately by weight:(a) 0.1 to 20% of a nonsoap anionicsurfactant; (b) 0.1 to 10% of a mixture of ##STR17## wherein w equalsone to four, and B is selected from the group consisting of hydrogen anda group represented by: ##STR18## wherein R is selected from the groupconsisting of alkyl group having 6 to 22 carbon atoms, and alkenylgroups having 6 to 22 carbon atoms, wherein at least one of the B groupsis represented by said ##STR19## R' is selected from the groupconsisting of hydrogen and methyl groups; x, y and z have a valuebetween 0 and 60, provided that (x+y+z) equals 2 to 100, wherein inFormula (I) the weight ratio of monoester/diester/triester is 40 to 90/5to 35/1 to 20, wherein the weight ratio of Formula (I) and Formula (II)is a value between 3 and 0.02; (c) 0 to 50% of a water soluble glycolether cosurfactant; (d) 0 to 10% of a water insoluble hydrocarbon orperfume; (e) 0 to 15% of magnesium sulfate heptahydrate; (f) 0 to 10.0%of a grease release agent wherein said grease release agent ischaracterized by the formula ##STR20## wherein R₁ is a methyl group andR₂, R₃ and R₄ are independently selected from the consisting of methylethyl and CH₂ CH₂ Y, where Y is selected from the group consisting ofCl, Br, CO₂ H, (CH₂ O)_(n) OH wherein n=1 to 10, OH, CH₂ CH₂ OH and X⁻is selected from the consisting of Cl, Br, methosulfate ##STR21## orwherein said grease release agent is a polyethylene glycol complexedwith said anionic surfactant and said polyethylene glycol has amolecular weight of 500 to 1,000, wherein the polyethylene glycol hasthe structure

    HO(CH.sub.2 CH.sub.2 O).sub.n H

wherein n is 11 to 52, or wherein said grease release agent is depictedby the formula: ##STR22## wherein n is 5 to 14, x is 7 to 19, w and zcan each be 5 wt. % to 95 wt. % and y is of such a value as to provide amolecular weight 10,000 to 30,000. or wherein said grease release agentis depicted by the formula: ##STR23## wherein x is hydrogen or an alkalimetal cation and n is a number from 2 to 16, R₁ is selected from thegroup consisting of methyl and hydrogen, R₂ is a C₁ to C₁₂, linear orbranched chain alkyl group and R₃ is a C₂ to C₁₆, linear or branchedchain alkyl group and y is of such a value as to provide a molecularweight of about 5,000 to about 15,000; and (g) the balance being water.